Aralkylated sulphamides and process of making same



, Patented Apr. 23, 1946 AnsLKYm'rEnsuLrnAMmEs AND.

rnocass or MAKING ssmn out Albrecht, Neuewelt, near Basel, Switzerland,

assignor to the Swiss firm of Society of Chemical Industry in Basic,Basel, Switzerland No Drawing. Application February 5, 1943, Serial No.474,900. In Switzerland January 19, 1942 4 claims. 401160-457) It hasbeen found that new sulphamide derivatives are obtained if sulphamideswhich contain at least one hydrogen atom belonging to a sulphamide groupare reacted with aralkylating agents and a water-solubilizing step iseffected in so far as the parent materials do not already containwater-solubilizing groups.

sulphamides which can be used are, for example, those of the aliphaticseries, such as ethane sulphonic acid amide, octane sulphonic acidamide, cetyl sulphonic acid amide, also mixtures of sulphamides such asare obtained bytreatment of aliphatic hydrocarbons with chlorine andsulphur dioxide, if desired, during irradiation with chemically activelight, and subsequent action of ammonia or of primary amines.Furthermore,

num chloride on tetrahydronaphthalene in known manner. Apart from thehalogen atomsalready mentioned, the sulphamides can also contain furthersubstituents, such as hydroxyl groups, amino groups, substituted-forexample acylated-amino groups, methoxy groups, etc. Examples of thesesubstituted sulphamides are N -monohydroxyalkylsulphamides, such asN-hydroxyethylcymene sulphamide.

As water-solubilizing groups, the sulphamides can contain, for example,sulphonic acid groups,

neutralized carboxyl, sulphuric acid ester, or thicsulphuric acidgroups. sulphonic acids and acid sulphuric acid esters contain sulphuricacid radicals as water-solubilizin groups. Such watersolubilizing groupscan be contained in a radical united to the sulphur atom of thesulphamide group, for example, in an aromatic nucleus, or

also in a radical united to the nitrogen atom of the sulphamide group.Examples of sulphamides of this nature are 4-(phenyl-sulphamino)-benzene-lpropyl-pheny1sulphamino) benzene-l-sulphonic acid,2-(3'-aminoph'enyl sulphamino) -naphthalens-6 8-disulphonic acid. Thesesulphamides are readily obtainable by reacting aryl sulphonic acidchloridesif desired, nitrated-such as cymene sulphonic acid,4-(1'-methyl-4'-isoacid chloride, with aminoarylsulphonic acids, such assulphanilic acid, z-aminonaphthalene- 6:8-disulphonic acid in" the usualmanner, it desired, with subsequent reduction of a nitro group. Thereaction products of primary sulphamides with halogencarboxylic acids,such as chloracetic acid, also with salts of aldehyde-bisulphitecompounds or of aldehyde-sulphoxylic acids also come i intoconsideration. Products of this nature are obtained for example, byheating sulphamides with solid sodium formaldehyde bisulphite to about150-200 'C., if desired, in the presence of secondary amines, or withdry sodium formaldehyde sulphoxylate to about mil-120 C., for example,according to the processes described in U. S. patent applications SerialNo. 447,145 (filed June 15, 1942) and Serial No. 443,662 (filed May 19,1942) The condensation products-of aminoarylsulphonic acids withchloroacetylated sulphamides also form suitable parent materials; as

representatives of this type of sulphamide mention may be made of'thecondensation products obtainable in the usual manner-of2-aminonaphthalene-S-sulphonic acid or of z-aminonaphthalene-6:8-disulphonic acid with N-chloracetylcymene sulphamide orN-chloracctyltetrahydronaphthalene sulphamide.

Particularly suitable for use as aralkylating agents are thechloromethyl compounds of arcmatic or partially hydrogenated aromaticcompounds, such as benzyl chloride, chloromethyltoluene,chloromethyl-xylene, chloromethyl-cumene, z-chloromethylcymene (cymylchloride),

l-chloromethyl-naphthalene, chloromethyltetra hydronaphthalenes, forexample, ar-z-chloromethyl-tetrahydronaphthalene,

treatment of the addition product of benzene and cyclohexene withformaldehyde, aqueous hydrowhich are not yet described in the literaturecan be prepared without trouble according to analogous processes, forexample, by introducing hydrcgen chloride gas into a mixture, heated to-70 (3., of the hydrocarbons, concentrated formaldehyde soltuion andconcentrated aqueous sulphonic acid chloride, 3-nitrobenzene sulphonichydrochloric acid, if necessary, plus an addition of zinc chloride,

As aralkylating agents chloromethyl derivatives of hyd'roxyarylcompounds, for example, the chloromethyl compound of the phenoldikeaddichloromethylcyclohexyl-benzene (obtainable, for example, by

tion product of phenol and dipentene, also chloro- 7 methyl compounds ofothers containing aryl radicals, such as the chloromethyl compound orthe ether obtained by condensation of dipentene with p-naphthol, alsocome into consideration. These chloromethyl compounds can be preparedfrom hydroxyaryl compounds and their ethers-some of which are described,some available directly by analogous processes-in the manner alreadydescribed above for the chloromethyl derivatives of hydrocarbons.

The reaction between the sulphamides and the aralkylating agentspreferably takes place at raised temperature, advantageously in thepresence of acid-binding agents, such as sodium hydroxide. It ispossible, for example, to react the aralkyl chloride with aqueoussolutions of the alkali salts of the sulphamides at 60-70 C., thesolution being maintained alkaline in reaction by adding sodiumhydroxide.

In order to introduce the water-solubilizing groups, the products of thepresent inventionso far as they still contain a hydrogen atom belongingto a sulphamide groupcan, for example, be reacted with halogencarboxylicacids, such as chloracetic acid, also with halogensulphonic acids, suchas bromethane sulphonic acid, preferably in the presence of acid-bindingagents, such as sodium hydroxide. Products which contain easilysulphonatable aromatic nuclei or hydroxyl groups,'for example,hydroxyethyl groups, can be made water soluble by treatment withsulphonating agents, such as concentrated sulphuric acid, additionproducts of sulphur trioxide and tertiary amines, Hyroxyethyl groups,for instance, may be transformed into acid sulphuric acid ester groupsby a sulphonation process under mild conditions, for instance; in thepresence of dlluents at a low temperature.

The products of the present invention may be designated as sulphamideswhich are substituted at the amide nitrogen atom by at least one aralkylradical containing at least 8 carbon atoms, which products are solid toliquid substances which are ing at least one water-solubilizing groupdifferingfrom the sulphamide group are in the form of the alkali metalsalts soluble to easily dlspersible in water. Products obtained with theaid of 2-chlor the formula are excellent wetting agents; productscontaining tetrahydronaphthylmethyl radicals are remarkable for theirgood washing action.

The products of the present invention can be used alone or inconjunction with other. substances, such as inorganic salts, which arecommonly usedgin combination with textile auxiliary 65-70" C. Stirringis continued at thg methyl oymene contain cymylmethyl radicals of C CHaThe reaction with ar-2-chlormethyl-tetrahydronaphthalene yieldsaralkylated sulphamides containing tetrahydronaphthylmethyl radicals ofthe formula I CH3- --S0aNa group.

products.

Example 1 7 parts oi the condensation product obtained by the reactionof cymene sulphamide with so-' dium formaldehyde-bisulphite of theprobable formula on C C-Ht are dissolved in 14 parts by volume of waterand 3.2 parts of ar-2-chloromethyl-tetrahydronaphthalene and 2.9 partsof sodium hydroxide solution of 30% strength are allowed to run into thesolution in the course of 1 hour whilst stirring at temperature givenfor some time, and the excess of sodium hydroxide is then neutralizedand the reaction mixture evaporated to dryness. The powder thus obtainedis dissolved by water to give a clear, foaming solution having goodwashing power.

It most probably corresponds to the formula The formula iSOaNa] for thewater-solubilizing group is intended to express that it is not knownwhether the CH2- group is bound to the sulphur atom or to an oxygen atomoi the In other words, it is uncertain whether the solubilizing group isbound according to the formula The condensation product of cymenesulphamide with sodium iormaldehyde-hisulphite used as parent materialcan be obtained by heating 53 parts of cymene sulphamide (a mixture ofthe isomeric sulphamides obtainable by converting cymene into thesulphochloride by means of chlorsulphonic acid and subsequent action ofammonia thereon), 50 parts of sodium formaldehyde-bismphite, and 2.5parts of diamylamine for about 20 minutes at -165 8-18 carbon atoms withsodium formaldehyde parts of cymene sulphamide (mixture of theisostrength are allowed to run into the solution in tr 1 d withsulphuric acid and evaporated to 20 which should giveaclear solution ondilution with P c h Obtained is a powder which is disthen stirred fora'time at the temperature given asoaoeo 3 The product obtainedby-condenaing a sulphand sodium formaldehyde-sulphoxylate used as amideof an aliphatic hydrocarbon containing parent material is obtainable byheating 10.6

sulphoxylate may be aralkylated with ar-2-chlormeric sulphamidesobtained by treating cymene methyltetrahydronaphthalene in a similarman- 5 with chlorosulphonic acid and subsequent action ner. of ammonia)with 8.5 parts of sodium formalde- Example 2 hyde-sulphoxylate for about20 minutes at 120 C. parts of the product obtained by thereactionExample 4 of tetrahydronaphthalene-sulphamide with so- 93 parts or theproduct obtained by reacting dium formaldehyde-bisulphlte are dissolvedin 2c 10 I by vol e of water d 4'4 I of tetrahydronaphthalenesulphamide, with sodium disso '20 chloroinethyl-tetrahydronaphthaleneand 3.9 fim g gzi gg a afigf gg ge's; parts Sdmm hydroxide of 30%chloromethyltetrahydronaphthalene and 4.8 parts of sodium hydroxidesolution of 30% the course of 2 hours whilst stirring at 65-70 strengthare allowed to run into the solution dur- The reaction mixture is thenstirred at the temg about 2 hours stirring. at 5 700 C- pieratiire givenuntil a samgleisgives 8?] 01 511 solu" stirring is continued for about 1hour at the temon n warm wa er, w c usu y e case after a short time. Themixture then new perature given, after which the reaction mixture,

water, is neutralized with sulphuric acid and evaporated to dry'nessJThe product thus obtained is an almost colourless power which dissolvesin warm water to give a foaming solution dryness. The product thusobtained, which is a readily pulverized, solid mass, dissolves in warmwater to yield a clear, foaming solution possessing good washing powers.It probably corresponds to of good washing power. It probablycorresponds the formula to the formula H 'n ens-{some H H K CHr-[80iNa]The reaction product of tetrahydronaphthalene The reaction product oftetrahydronaphsulphemide e sodium formeldehvde-bisulphite thalenesulphamide with sodium formaldehydeused as Parent material can beobtained y heat sulphoxylate mentioned, above can be obtained l 21 Partsof tetrahydlonapmhalene sulpham' 40 by heating 10.5 parts .oftetrahydronaphthalene lde Of the isomeric Obtalnof isomeric sulphable ytreating fetl'ahydmnaphthalene with. amides obtained by treatment oftetrahydroe uln c a and subsequently reacting naphthalene withchlorsulphonic acid and subthe product with ammonia) P of sodium sequentreaction with ammonia) with 6.5 parts formaldehyde-bisulphite and 1.2parts of diam of anhydrous sodium formaldehyde-sulphoxylate amine forabout 1 hour at ISO-165 C. for about 20 minutes 1 5.120 C Example 3Example 5 10 Parts f th P oduct bt ined by reacting 7.2 parts of thereaction product of sodium ym ne sulphamide with sodium formaldehyde-1formaldehyde sulphoxylate with the sulphamide ph y t ar i so ved in 2parts y Volume obtained from a mixture of polycyclic, partially ofwater, and 5.8 parts 0! technical chloromethylhydrogenated aromatichydrocarbons are ,disym ne an -1 parts of sodium hydroxi 111- solved in14 parts by volume of water, and 3-6 tion of 30% strength are allowed torun in during parts of ar 2-chloromethyltetrahydronaphabOllt /2 h r Wils ir in at -7 S i thalene and 3.2 parts of a solution of sodium ring in n ed f r some ime at he mperahydroxide of 30% strength are allowed torun ture i e wh n the mix e i neu a i d wi h into the solution in thecourse of 2 hours whilst su phu ic acid and evap t dryness. The stirringat -70" 0. The reaction mixture is solved by Warm W t r t yield afoaming Solu i n until the reaction productis soluble in water to f oodwetting and washing p w It P ly a clear solution, which usually takes ashort corresponds to the formula I time. The alkaline reaction solutionis then CH v neutralized and evaporated to dryness, a solid,-

easily pulverized mass being obtained which discm-{somq u solves in warmwater to yield a foaming solu- SOPN/ Cm 2221 of good washing power,especially towards The condensation product, obtained by the use Rv k ofsodium formaldehyde-sulphoxylate, which is g 1 used as parent materialcan be prepared a" C follows:

CH Tetrahydronaphthalene is partially converted g in known manner into amixture of highly condensed, polycyclic and partially hydrogenated Thereaction roduct or cymene sulphamide u yd ocar ons, containing anionsother thin I technical threne, by heating with aluminium chloride at 100C. and is freed from low boiling point constituents (benzene andtetrahydronaphthalene). The mixture of higher hydrocarbons thus obtainedis thereupon converted into a mixture of sulphonlc acid chlorides by theaction of chlorosulphonic acid at --5 to -'10 C. and, subsequently, intoamixture of sulphamides by the action of aqueous ammonia. 2 parts of themixture of sulphamides thus obtained are then heated with 1.4 parts ofanhydrous sodium formaldehyde-sulphoxylate for about V hour at Example 620.8 parts of the sodium salt of tetrahydronaphthalene-sulphaminoacetlcacid are dissolved in 30 parts of water, and 12.8 parts of ar-2- n H o Hcm-c-oNa sow-N n H n H n on i The sodium salt oftetrahydronaphthalenesulphaminoaoetic acid used as parent material canbe prepared in known manner by treating tetrahydronaphthalene sulphamidewith chloroacetic acid in aqueous alkaline solution.

Example '7 A solution of 3.5 parts of chlorosulphonc acid in 10 parts byvolume of ether is dropped during hour at 0-5 G. into a solution of 10parts N- hydroxyethyl N cymylmethyl-cymene sulphamide in 10 parts byvolume of ether. The reaction mixture is then stirred for 2. hours at20-25 C. and is allowed to stand. overnight, after which it is pouredinto water and neutralized with sodium hydroxide solution. Solid sodiumchloride is now added. The sodium salt of the new sulphuric acid esterwhich has been obtained by salting out is a solid, pulverizablemass whendry and is dissolved by warm water to yield a'clear, foaming solution ofhigh wetting power.

' an addition of sodium sulphate is advisable when using it as a wettingagent. The new product corresponds to the formula 1 a CE:

| CHi 2,808,990 'octahydroanthracene and octahydrophenan TheN-hydroxyethyl N cymylmethylcymene sulphamide mentioned above can beprepared as follows:

41.4 parts of N-hydroxyethylcymene sulphamide of the formulaSOr-NH-CHa-C Hr-OH CH: CH:

obtained by the conversion of cymene into the mixture oi the twoisomeric sulphonic acid chlorides by means of chlorosulphonic acid andsubsequent reaction with monoethanolamine, are dissolved in 300 parts byvolume of alcohol; 26.6 parts of a solution of sodium hydroxide of 30%strength are added, and 36.5 parts of 2-chloromethylcymene (obtained,for example, by introducing hydrogen chloride gas into a mixtureofcymene, formaldehyde and concentrated hydroamide thus obtained isdried. Instead of N-hydroxyethyl-N-cymylmethyl-cymene sulphamide thecorresponding N-tetrahydronaphthylmethyl derivative or the N-hydroxyethyl-N-cymylmethyl tetrahydronaphthalene sulphamide may betreated with chiorsulfonic acid in a similar manner.

Example 8 15 parts of the condensatlonproduct obtained from the disodiumsalt of 2-aminonaphthalene- 6:8-disulphonic acid andmonochloracetyl-tetrahydronaphthalene sulphamide of the formula aredissolved in about 25 parts by volume of water at 70 0., and 4.5 parts(1 mol) of ar-2-chloromethyltetrahydronaphthalene and 3.7 parts ofsodium hydroxide solution of 30% strength are introduced during 1 hourwhilst stirring at about -70" C. After stirring for about V hour, thereaction product gives a clear solution in water. A further 4.5 parts ofar-2-chloromethyltetrahydronaphthalene (1 mol) and 3.7 parts of sodiumhydroxide solution of 30% strength are then added at the sametemperature in the course of about Y2 hour. Alter stirring for about afurther 2 hours at Bil- C. the reaction product gives a clear solutionin water. After drying. the new condensation product is a solid. pulver-7. izable mass which dissolves in water to give a asoacoo clear, foamingsolution ot'good washing powers. It most probably corresponds to theformula NBOIS The above mentioned condensation product of the disodiumsalt of 2-aminonaphthalene-6:8- disulphonic acid andmonochloracetyltetrahydronaphthalene sulphamide can be prepared in thefollowing manner:

46 parts of t'etrahydronaphthalene sulphamide, obtained by treatment oftetrahydronaphthalene with chlorosulphonic acid and subsequent reactionof the mixture of isomeric sulphonic acid chlorides thus obtained withammonia, are heated with 24.6 parts of chloracetyl chloride in thecourse of 2 hours to about 100 C., and heating is continued for about afurther 3 hours at the same temperature. 14.4 parts of the chloracetylderivative thus obtained are mixed with 6.7 parts of a sodium hydroxidesolution of 30% strength and 7.5 parts by volume of alcohol and aredropped into a solution of 24.3 parts of acid sodium 2:6:8-naphthylaminedisulphonate (containing 62.4% free disulphonic acid) in about 50 partsby volume of water, which has been neutralized with sodium carbonate, inthe course oi. 2 hours whilst stirring at 65-70 C; The reaction liquormust be maintained in a slightly alkaline condition by addition ofsodiumhydroxide solution. Stirring is continued for a further 2 hours at thetemperature stated, care being, taken that the weakly alkaline reactionis maintained, and the reaction product, which gives a clear solution inwater, is then evaporated to dryness.

The 1:5-amino naphthalene sulphonic acid instead of the 2:6:8-aminonaphthalene disulohonic acid maybe treated in a similar manner. 7

Example 9 In order to wash 50 kgs. of woolen yarn, a bath is preparedcontaining 1 gm. of the product of Example 8 per litre of water at 45 C.(liquor ratio 1:20). The material is entered into the bath, turned forti hour and rinsed. After this treat- 01 the mixture v Q 5 mentthewoolen yarn is excellently clean and can be dyed directly withoutdimculty.

What I claim is: 1. An alkali metal salt formula A r-S O N CHa-arHwherein Ar represents a member selected from the group consisting ofphenyl, p-tolyl, xylyl, cymyl and chlorocymyl, CI-Iz-aryl represents anaralkyl radical selected from the group consisting of myl thyl andtetrahydronaphthylmethyl, and X is an alkyl radical containing awater-solubilizing group selected from the class consisting of sulphonicacid groups, sulphinic acid group and sulphuric acid ester groups.

2. An alkali metal salt of the acid sulphuric acid ester of the formula(ID-H:

/ClhCIIr0-SO:H SOr-N CH:

CH: Cg Cg; CH3

CH3 CHI 3. An alkali metal salt of the sulphamide of the formula 4. Analkali metal salt of the sulphamide of the formula CHr-{BOzNifl 50:- CH;

CH 3 Cs CH3 5 Cl CH;

o'rro ALBRECHT;

of a sulphamide of the Certificate of Correction Patent No. 2,398,990.April 23, 1946:.

OTTO ALBRECHT It is hereby certified that errors appear in the printedspecification of the above numbered patent reguiring correction asfollows: Page 2, second column, lines 43 to 49, Example 1, for atportion of the formula reading y n n p n G H .C

read H H page 3, second column, line 28, Example 4, for that portion ofthe formula reading and that the said Letters Patent should he read withthese corrections therein that the same may conform to the record of thecase in the Patent Ofiice.

Signed and sealed this30th day of July, A. D. 1946.

LESLIE FRAZER,

First Assistant Commissioner of Patents.-

